CN111424257B - Three-dimensional reticular graphene with biomass structure and preparation method thereof - Google Patents
Three-dimensional reticular graphene with biomass structure and preparation method thereof Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
Abstract
The invention belongs to the field of preparation of three-dimensional reticular graphene, and particularly relates to three-dimensional reticular graphene with a biomass structure and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, carbonizing a biomass template; secondly, plating nickel on the surface of the carbonized biomass material; thirdly, carrying out chemical vapor deposition reaction to grow graphene; fourthly, placing the sample into a dilute hydrochloric acid solution to remove the nickel matrix; and fifthly, drying to obtain the three-dimensional reticular graphene with the biomass structure. The method is mainly used for preparing the three-dimensional reticular graphene with the biomass structure, and the three-dimensional graphene with adjustable structure and shape can be prepared.
Description
Technical Field
The invention belongs to the field of preparation of three-dimensional reticular graphene, and particularly relates to three-dimensional reticular graphene with a biomass structure and a preparation method thereof.
Background
The graphene is formed by sp carbon atoms2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. The material is the highest-strength material known at present, and has excellent electric conduction and heat conduction performance, extremely high electron mobility and ultrahigh flexibility. Graphene has considerable development potential, has wide development space in the fields of electronics, energy, catalysis and the like, and is one of new materials which are expected by people most in the 21 st century. But due to the agglomeration and aggregation caused by the van der waals force between the graphene, the performance of the graphene is greatly reduced. The three-dimensional graphene has the advantages of two-dimensional graphene, and the graphene has a large specific surface area and high porosity due to the unique network structure. Therefore, the performance of the graphene in the aspects of electrode materials, catalytic materials and the like is greatly improved.
At present, the fields of the most intense heat of graphene application have the aspects of super capacitors, water pollution treatment, transistors, touch screens and the like, and the graphene structures, performances and forms required by various application fields have different requirements, so that how to produce and prepare the adjustable structure, the graphene in the form becomes the most urgent problem to break through at present.
Disclosure of Invention
The invention provides three-dimensional reticular graphene with a biomass structure and a preparation method thereof, and the three-dimensional reticular graphene with an adjustable structure and shape can be prepared.
The technical scheme adopted by the invention is as follows:
a preparation method of three-dimensional reticular graphene with a biomass structure comprises the following steps:
s1, carbonizing the biomass to obtain a carbonized biomass material, and slicing the carbonized biomass material to obtain a flaky carbonized biomass material;
s2, preparing electroplating solution with nickel salt as main salt;
s3, putting the sheet carbonized biomass material into an electroplating solution taking nickel salt as main salt for electroplating, covering a nickel layer inside the pore channels in the sheet carbonized biomass material, and then removing the carbonized biomass material to obtain a sample consisting of nickel oxide;
s4, depositing graphene on the sample obtained in the S3;
and S5, removing the nickel oxide of the sample deposited with the graphene to obtain the three-dimensional reticular graphene with the biomass structure.
When the biomass is carbonized, the temperature is raised from the room temperature to 350-600 ℃ at the temperature rise speed of 1-20 ℃/min under the argon atmosphere, the temperature is preserved for 1-2 hours, then the temperature is raised to 700-plus-material 1000 ℃ at the temperature rise speed of 1-20 ℃/min, the temperature is preserved for 1-3 hours, and then the biomass is cooled to the room temperature along with the furnace to obtain the carbonized biomass material.
The electroplating solution is prepared by dissolving main salt, a buffering agent and a surfactant in deionized water, wherein:
the main salt is one or a mixture of nickel nitrate, nickel chloride, nickel sulfate and nickel acetate; the buffer is boric acid, citric acid, acetic acid, citrate or acetate; the surfactant is sodium dodecyl benzene sulfonate, sodium octyl sulfate or sodium 2-ethyl sulfate.
The main salt adopts nickel chloride, the buffering agent adopts boric acid, the surfactant adopts sodium dodecyl sulfate, the concentration of the nickel chloride in the electroplating solution is 20-40g/L, the concentration of the boric acid is 3-10g/L, and the concentration of the sodium dodecyl sulfate is 0.005-0.02 g/L.
During electroplating, the current density is 10-50mA/cm2The electroplating time is 5-15 h.
The carbon source for depositing graphene is methane, ethane, toluene, acetylene, propylene, ethanol or tartaric acid.
The carbon source during graphene deposition is methane, and during graphene deposition, the sample is placed into a tube furnace and heated to 550-700 ℃ in the argon atmosphere; then introducing H2Wherein the flow rate of argon gas is 100-200sccm, and the flow rate of hydrogen gas is 10-50 sccm; after the heat preservation is carried out for 2-3 hours, the temperature is raised to 950-.
When removing nickel oxide of a sample deposited with graphene, dripping a PMMA solution with the solute mass fraction of 3% -7% on the sample after the graphene is grown, putting the sample into a 0.5-2mol/L HCl solution after drying, putting the sample into an acetone solution after 12-24h to remove PMMA, and drying to obtain the three-dimensional reticular graphene with the biomass structure.
The biomass is selected from the group consisting of northeast China ash, Korean pine, Zelkova, birch, Pinus sylvestris, poplar, elm, cypress, paulownia or poplar, and the thickness of the sheet carbonized biomass material is 0.5-2 mm.
The three-dimensional reticular graphene with the biomass structure is prepared by the preparation method.
The density of the three-dimensional reticular graphene with the biomass structure is 0.2-0.7g/cm3。
The invention has the following beneficial effects:
the preparation method of the three-dimensional reticular graphene with the biomass structure comprises the steps of taking biomass as a raw material, carbonizing and slicing the biomass, plating nickel on the surface of a flaky carbonized biomass material, carrying out chemical vapor deposition reaction to grow graphene, and removing a nickel substrate to obtain the three-dimensional reticular graphene with the biomass structure. The nickel electroplating is to ensure that the biomass has the activity of catalyzing the growth of graphene. The preparation method is simple in preparation process, the prepared three-dimensional reticular graphene has a unique biomass structure, and the three-dimensional reticular graphene with different appearances can be prepared by utilizing biomass templates which are abundant in nature. The technological process has good expansibility, and biomass materials in nature can be prepared into three-dimensional reticular graphene with corresponding structures by the method. Meanwhile, the preparation method provided by the invention can lower the density of the three-dimensional reticular graphene. The density drop is reduced compared to graphitized biomass of the same structure, and the current collector used as a supercapacitor can load more active material with less mass, thereby increasing the energy density of the supercapacitor.
Furthermore, when the biomass is carbonized, the temperature rises from room temperature to 350-600 ℃ at the temperature rise speed of 1-20 ℃/min in the argon atmosphere, the temperature rise speed is controlled because the overhigh temperature rise speed can cause large thermal stress and damage the integrity of the material, and the pre-carbonization temperature is controlled because grease organic matters in the biomass can volatilize in the temperature range to generate large structural change.
Furthermore, the uniformity and compactness of the coating can be influenced by the current density, and the integrity of the structural grown graphene can be influenced by the reduction of the uniformity and compactness of the coating caused by the overhigh current density, so that the current density is 10-50mA/cm during the re-electroplating process of the invention2The electroplating time is 5-15h, and the nickel layer obtained by electroplating is relatively uniform and has relatively good compactness, so that the deposited graphene is more uniform.
Further, when removing the nickel oxide of the sample deposited with the graphene, dropping a PMMA solution on the sample after the graphene is grown, wherein the purpose of dropping the PMMA solution is to protect the integrity of the graphene when the nickel matrix is removed.
The three-dimensional reticular graphene with the biomass structure has various structures and forms, can meet the requirements of different aspects such as a super capacitor, water pollution treatment, a transistor, a touch screen and the like, and has lower density and wide application value.
Drawings
FIG. 1 is a flow chart of a method for preparing three-dimensional reticular graphene with a biomass structure according to the present invention;
fig. 2 is an SEM scan of the pinus sylvestris structure three-dimensional graphene network perpendicular to the growth direction in the embodiment of the present invention;
fig. 3 is an SEM scan of the pinus sylvestris structure three-dimensional graphene network parallel to the growth direction in the embodiment of the present invention;
fig. 4 is an SEM scan of a three-dimensional network graphene fracture site of the pinus sylvestris structure in an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
The invention adopts biomass material as a template to prepare the three-dimensional reticular graphene. The three-dimensional reticular graphene prepared by the method has a complex structure made of a biomass material, and the structure is kept complete. The size of the formed three-dimensional reticular graphene can be accurately controlled by controlling the size of the template.
Referring to fig. 1, the preparation method of three-dimensional reticular graphene with a biomass structure of the present invention is completed by the following steps:
firstly, carbonizing a biomass material: preparing a biomass material, raising the temperature of the biomass material from room temperature to 350-600 ℃ at the temperature raising speed of 1-20 ℃/min under the argon atmosphere, preserving the heat for one to two hours, raising the temperature to 1000 ℃ at the temperature raising speed of 1-20 ℃/min, and preserving the heat for 1-3 hours. And then cooling to room temperature along with the furnace to obtain the carbonized biomass material. The carbonized biomass material is cut into slices with the thickness of 0.5-2mm for standby.
Secondly, preparing an electroplating liquid template: dissolving main salt, a buffering agent and a surfactant in deionized water, and stirring to obtain the electroplating solution.
And thirdly, enabling the carbonized biomass template (namely the sheet cut by the carbonized biomass material) to have catalytic activity: and (3) placing the biomass template prepared in the first step into the electroplating solution prepared in the second step for electroplating, so that a layer of metallic nickel is completely covered inside the pore channel in the biomass template. And then putting the biomass matrix into a muffle furnace to remove the biomass matrix. A sample having the same structure as the biomass template and made of nickel oxide was obtained.
Fourthly, depositing graphene: putting the sample prepared in the third step into a tube furnace, and raising the sample in an argon atmosphereThe temperature is 550-700 ℃. Then introducing H2Wherein the flow rate of argon gas is 100-200sccm, and the flow rate of hydrogen gas is 10-50 sccm. After the temperature is kept for two to three hours, the temperature is raised to 950-4. Wherein the flow rate of the methane is 1-40 sccm. Stopping introducing the methane after the methane is deposited for 5-20min, and cooling to room temperature at the cooling speed of 5-15 ℃/min.
Fifthly, removing the nickel matrix: dropping a plurality of drops of PMMA solution with solute mass percent of 4% on the sample after the graphene is grown, and putting the sample into 0.5-2mol/L HCl solution after the sample is dried. And after 12-24 hours, putting the sample into an acetone solution to remove PMMA. And drying to obtain the three-dimensional reticular graphene with the biomass structure.
As a preferred embodiment of the present invention, the biomass material may be one of ash, red pine, zelkova, birch, pinus sylvestris, poplar, elm, cypress, paulownia, and poplar.
As a preferred embodiment of the invention, the main salt is one or a mixture of several of nickel nitrate, nickel chloride, nickel sulfate and nickel acetate according to different proportions; the buffer is boric acid, citric acid, acetic acid, citrate or acetate, and the surfactant is sodium dodecyl benzene sulfonate, sodium octyl sulfate or sodium 2-ethyl sulfate.
As a preferred embodiment of the present invention, the carbon source may also be ethane, toluene, acetylene, propylene, ethanol or tartaric acid.
The preparation method of the three-dimensional reticular graphene by taking the pinus sylvestris as the carbonized biomass material comprises the following steps:
firstly, carbonizing a biomass material: preparing a biomass material, raising the temperature of the biomass material from room temperature to 450 ℃ at the temperature raising speed of 2 ℃/min in an argon atmosphere, preserving the heat for two hours, raising the temperature to 850 ℃ at the temperature raising speed of 2 ℃/min, and preserving the heat for three hours. And then cooling to room temperature along with the furnace to obtain the carbonized biomass material. It was cut into 2mm thick sheets for use.
Secondly, preparing an electroplating liquid template: dissolving nickel chloride, boric acid and sodium dodecyl sulfate in deionized water, wherein the concentration of the nickel chloride is 35g/L, the concentration of the boric acid is 7g/L, and the concentration of the sodium dodecyl sulfate is 0.01 g/L. Stirring to obtain the electroplating solution.
Thirdly, enabling the carbonized biomass template to have catalytic activity: and (3) placing the biomass template prepared in the first step into the electroplating solution prepared in the second step for electroplating, so that a layer of metallic nickel is completely covered inside the pore channel in the biomass template. The current density is 20mA/cm2The plating time was 10 h. And then putting the biomass matrix into a muffle furnace to remove the biomass matrix. A sample having the same structure as the biomass template and made of nickel oxide was obtained.
Fourthly, depositing graphene: and (4) putting the sample prepared in the third step into a tube furnace, and heating to 600 ℃ under the argon atmosphere. Then introducing H2Wherein the flow rate of argon gas is 200sccm, and the flow rate of hydrogen gas is 50 sccm. Keeping the temperature for two hours, then raising the temperature to 1050 ℃ and introducing CH4. Wherein the flow rate of methane is 10 sccm. The methane was stopped after 10min of methane deposition and brought to room temperature at a cooling rate of 15 ℃/min.
Fifthly, removing the nickel matrix: dropping a plurality of PMMA solutions with the mass fraction of 4% on the sample after the graphene grows, and putting the sample into 1mol/L HCl solution after the sample is dried. After 24h the sample was placed in acetone solution to remove the PMMA. Obtaining the three-dimensional reticular graphene with the pinus sylvestris structure.
The method for preparing the three-dimensional reticular graphene by taking the Korean pine as the carbonized biomass material comprises the following steps:
firstly, carbonizing a biomass material: preparing a biomass material, raising the temperature of the biomass material from room temperature to 600 ℃ at the heating rate of 1 ℃/min in an argon atmosphere, preserving the heat for one hour, raising the temperature to 700 ℃ at the heating rate of 1 ℃/min, and preserving the heat for two hours. And then cooling to room temperature along with the furnace to obtain the carbonized biomass material. It was cut into 0.5mm thick sheets for use.
Secondly, preparing an electroplating liquid template: dissolving nickel chloride, boric acid and sodium dodecyl sulfate in deionized water, wherein the concentration of the nickel chloride is 20g/L, the concentration of the boric acid is 3g/L, and the concentration of the sodium dodecyl sulfate is 0.005 g/L. Stirring to obtain the electroplating solution.
Thirdly, the carbonized biomass template has catalytic activity: and (3) placing the biomass template prepared in the first step into the electroplating solution prepared in the second step for electroplating, so that a layer of metallic nickel is completely covered inside the pore channel in the biomass template. The current density is 10mA/cm2The plating time was 15 h. And then putting the biomass matrix into a muffle furnace to remove the biomass matrix. A sample having the same structure as the biomass template and made of nickel oxide was obtained.
Fourthly, depositing graphene: and (4) putting the sample prepared in the third step into a tube furnace, and heating to 550 ℃ under the argon atmosphere. Then introducing H2Wherein the flow rate of argon gas is 100sccm, and the flow rate of hydrogen gas is 10 sccm. Keeping the temperature for two hours, then raising the temperature to 950 ℃ and introducing CH4. Wherein the flow rate of methane is 1 sccm. The methane was stopped after 20min of methane deposition and brought to room temperature at a cooling rate of 10 ℃/min.
Fifthly, removing the nickel matrix: dropping a plurality of PMMA solutions with the mass fraction of 4% on the sample after the graphene is grown, and putting the sample into 0.5mol/L HCl solution after the sample is dried. After 12h the sample was placed in acetone solution to remove the PMMA. Obtaining the three-dimensional reticular graphene with the Korean pine structure.
The preparation method of the three-dimensional reticular graphene by using the fraxinus mandshurica as the carbonized biomass material comprises the following steps:
firstly, carbonizing a biomass material: preparing a biomass material, raising the temperature of the biomass material from room temperature to 350 ℃ at a temperature rise speed of 20 ℃/min in an argon atmosphere, preserving the heat for two hours, raising the temperature to 1000 ℃ at a temperature rise speed of 1 ℃/min, and preserving the heat for two hours. And then cooling to room temperature along with the furnace to obtain the carbonized biomass material. It was cut into 2mm thick sheets for use.
Secondly, preparing an electroplating liquid template: dissolving nickel chloride, boric acid and sodium dodecyl sulfate in deionized water, wherein the concentration of the nickel chloride is 40g/L, the concentration of the boric acid is 10g/L, and the concentration of the sodium dodecyl sulfate is 0.02 g/L. Stirring to obtain the electroplating solution.
Thirdly, enabling the carbonized biomass template to have catalytic activity: placing the biomass template prepared in the first step into the electroplating solution prepared in the second step for electroplating, so that the inside of the pore channel in the biomass template is completely covered with a layerMetallic nickel. The current density is 50mA/cm2The plating time was 5 h. And then putting the biomass matrix into a muffle furnace to remove the biomass matrix. A sample having the same structure as the biomass template and made of nickel oxide was obtained.
Fourthly, depositing graphene: and (4) putting the sample prepared in the third step into a tube furnace, and heating to 700 ℃ under the argon atmosphere. Then introducing H2Wherein the flow rate of argon gas is 150sccm, and the flow rate of hydrogen gas is 25 sccm. Keeping the temperature for two hours, then heating to 1150 ℃ and introducing CH4. Wherein the flow rate of methane is 40 sccm. After 5min of methane deposition, the introduction of methane was stopped and the temperature was brought to room temperature at a cooling rate of 5 ℃/min.
Fifthly, removing the nickel matrix: dropping a plurality of PMMA solutions with the mass fraction of 4% on the sample after the graphene grows, and putting the sample into 2mol/L HCl solution after the sample is dried. After 18h the sample was placed in acetone solution to remove the PMMA. And obtaining the three-dimensional reticular graphene with the fraxinus mandshurica pine structure.
SEM scans of the three-dimensional graphene network prepared in the above examples are shown in fig. 1 to 3. Fig. 1 is an overall morphology diagram of three-dimensional network graphene prepared by using pinus sylvestris as a template, and it can be seen from the diagram that the prepared three-dimensional network graphene completely reproduces the tissue structure of the pinus sylvestris. Fig. 2 is a scanned graph of three-dimensional graphene network prepared by using pinus sylvestris as a template, which is parallel to the growth direction. The pipeline structure of the three-dimensional reticular graphene can be seen clearly from the figure, and the pipeline structures can be used as a transport channel of electrolyte in the super capacitor, so that the rate capability of the super capacitor is improved. Fig. 3 is a scanned view of a fracture of three-dimensional graphene network prepared by using pinus sylvestris as a template, and it can be seen from the scanned view that the whole three-dimensional graphene has the same shape as the pinus sylvestris, but has more channels for ion transmission. Compared with carbonized pinus sylvestris, the three-dimensional reticular graphene prepared by the embodiment has quite low density, and the density is reduced by two thirds; the density of the grown three-dimensional graphene can be controlled by controlling the flow of methane in the embodiment, and can be controlled to be 0.2g/cm3-0.7g/cm3。
Claims (10)
1. A preparation method of three-dimensional reticular graphene with a biomass structure is characterized by comprising the following steps:
s1, carbonizing the biomass to obtain a carbonized biomass material, and slicing the carbonized biomass material to obtain a flaky carbonized biomass material;
s2, preparing electroplating solution with nickel salt as main salt;
s3, putting the sheet carbonized biomass material into an electroplating solution taking nickel salt as main salt for electroplating, covering a nickel layer inside the pore channels in the sheet carbonized biomass material, and then removing the carbonized biomass material to obtain a sample consisting of nickel oxide;
s4, depositing graphene on the sample obtained in the S3;
and S5, removing the nickel oxide of the sample deposited with the graphene to obtain the three-dimensional reticular graphene with the biomass structure.
2. The method as claimed in claim 1, wherein the temperature is increased from room temperature to 350-600 ℃ at a rate of 1-20 ℃/min under argon atmosphere, the temperature is maintained for 1-2 hours, then the temperature is increased to 700-1000 ℃ at a rate of 1-20 ℃/min, the temperature is maintained for 1-3 hours, and finally the biomass material is cooled to room temperature along with the furnace to obtain the carbonized biomass material.
3. The method for preparing three-dimensional reticular graphene with a biomass structure according to claim 1, wherein the electroplating solution is prepared by dissolving main salt, a buffer and a surfactant in deionized water, wherein:
the main salt is one or a mixture of nickel nitrate, nickel chloride, nickel sulfate and nickel acetate; the buffer is boric acid, citric acid, acetic acid, citrate or acetate; the surfactant is sodium dodecyl benzene sulfonate, sodium octyl sulfate or sodium 2-ethyl sulfate.
4. The method according to claim 3, wherein the main salt is nickel chloride, the buffer is boric acid, the surfactant is sodium dodecyl sulfate, the concentration of nickel chloride in the electroplating solution is 20-40g/L, the concentration of boric acid in the electroplating solution is 3-10g/L, and the concentration of sodium dodecyl sulfate is 0.005-0.02 g/L.
5. The method for preparing three-dimensional reticular graphene with a biomass structure according to claim 1, wherein the current density is 10-50mA/cm during electroplating2The electroplating time is 5-15 h.
6. The method for preparing three-dimensional reticular graphene with a biomass structure according to claim 1, wherein a carbon source for depositing graphene is methane, ethane, toluene, acetylene, propylene, ethanol or tartaric acid.
7. The method for preparing three-dimensional reticular graphene with a biomass structure as claimed in claim 6, wherein the carbon source during graphene deposition is methane, and during graphene deposition, the sample is placed in a tube furnace, and the temperature is raised to 550-700 ℃ under the argon atmosphere; then introducing H2Wherein the flow rate of argon gas is 100-200sccm, and the flow rate of hydrogen gas is 10-50 sccm; after the heat preservation is carried out for 2-3 hours, the temperature is raised to 950-.
8. The method for preparing three-dimensional reticular graphene with a biomass structure according to claim 1, wherein when removing nickel oxide from a sample deposited with graphene, after the graphene grows, dropping a PMMA solution on the sample, after drying, putting the sample into a 0.5-2mol/L HCl solution, after 12-24h, putting the sample into an acetone solution to remove PMMA, and drying to obtain the three-dimensional reticular graphene with the biomass structure.
9. The method of claim 1, wherein the biomass is selected from the group consisting of ash, Korean pine, Zelkova, birch, Pinus sylvestris, Populus tremula, Ulmus pumila, cypress, Paulownia fortunei and Populus euphratica, and the sheet carbonized biomass material has a thickness of 0.5-2 mm.
10. Three-dimensional graphene network having a biomass structure prepared by the preparation method of any one of claims 1 to 9.
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